CN104262780B - A kind of with RE phosphate glass be light toner Ultraluminescence green plastic sheeting preparation method and in the application of false proof aspect - Google Patents

Abstract

A kind of with RE phosphate glass be light toner Ultraluminescence green plastic sheeting preparation method and in the application of false proof aspect, for problems such as doping type Rare earth fluorescent polymer material such as inorganic rare earth fluorescent agent and macromolecular material polarity spectrum big, rare-earth fluorescent concentration quenching, fluorescent stability, with phosphate glass as substrate, Tb³⁺Ion is luminescent activator, Ce³⁺Ion is sensitizer, by phosphate glass substrate and Tb in formula³⁺And Ce³⁺Cooperative effect, overcome fluorescence intensity quenching phenomenon, improve addition and the fluorescence efficiency of rare earth element tb；Cooling down glass preform machine pressed glass fragment with fusion method and mixture of ice and water, then airflow milling high pressure abrasive is prepared for the granularity phosphate glass less than 300nm: Tb³⁺, Ce³⁺Fluorescent material；Add surface modifier, by fluorescent material and polymer master batch melt blending, the plastic sheeting white clear in the sunlight that blown film obtains, under ultraviolet light irradiates, send beautiful green light, it is special through spectrum, as Anti-fake packaging film, antifalsification label printing element and anti-fake safety line base material to have.

Description

A kind of with RE phosphate glass be light toner Ultraluminescence green plastic sheeting preparation method and in the application of false proof aspect

Technical field

The present invention relates to a kind of with RE phosphate glass be light toner Ultraluminescence green plastic sheeting preparation method and in the application of false proof aspect, belong to rare earth high polymer material field and anti-counterfeit field.

Background technology

Rare earth element is added the method in macromolecular material and is substantially divided into two kinds: (1) rare earth compound is evenly dispersed in monomer or polymer as adulterant, form the rare earth high polymer existed with doping way, referred to as doping type rare earth high polymer.(2) first synthesize by the way of chemical bonding the rare-earth complex monomer of polyreaction can occur, then it is polymerized with other organic monomers and obtains high-molecular copolymer, or rare earth ion and ligand groups on macromolecular chain such as carboxyl, sulfonic group react and obtain rare earth high polymer complex, and rare earth ion is present in macromolecular material with bonding pattern.It is referred to as bonding type rare earth high polymer.

The fluorescent characteristic of rare earth element is mostly derived from the f orbitals electronics of the underfill of its internal layer.On the one hand, f orbitals electronics is shielded by 5s5p outer-shell electron, is affected little by outer layer.Therefore, improve rare earth doped compound content in macromolecule matrix and just can improve the fluorescence property of doping macromolecular material.And on the other hand, the abundant f unoccupied orbital having due to rare earth ion, ligancy higher (6-12), therefore during content of rare earth content height, easily form ion cluster, fluorescence intensity quenching phenomenon occurs, thus is difficult to obtain the rare earth high polymer material of high fluorescent.Select environment residing for suitable rare earth ion (ligand of rare earth ion or referred to as substrate) to obtaining high fluorescence efficiency and high fluorescent is particularly significant.

Secondly, most rare earth compound polarity is big, and the compatibility between the less organic polymer of polarity is bad, and especially rare earth inorganic matter is little with resin affinity, causes the Polymer Mechanical hydraulic performance decline of doped with rare-earth elements, transparency reduction.The main method solving this problem is to use effective technical method reduce rare earth mineral surfaces polarity and introduce coupling agent.

Rare earth luminous efficiency depends on the match condition of part lowest excited triplet energy level position and rare earth ion vibration level, the excited triplet state energy level of phosphate glass substrate and Tb^{3 +}Excited level coupling is preferably.Ce³⁺Be co-doped with substantially increasing the UV Absorption of sample, the notable sensitization near-infrared luminous efficiency of sample.

Summary of the invention

It is an object of the invention to simple formulation phosphate glass as substrate, with Tb³⁺Ion is photosensitizer, Ce³⁺Ion is as sensitizer, by phosphate glass substrate, Tb³⁺Ion and Ce³⁺Cooperative effect, first prepare formation be beneficial to Tb³⁺Luminous phosphate fluorescent glass.The levigate glass dust to mean diameter less than 300nm of characteristic airflow milling utilizing phosphate glass intensity low, crisp, then obtains the green false-proof film of Ultraluminescence with high-luminous-efficiency with plastic master batch melt blending blown film.

Concrete preparation method is as follows, and glass formula conversion for mass percent oxide is: P₂O₅50-90%；Li₂O 0-10%；Na₂O 5-25%；K₂O 0-15%；Tb₂O₃1-15%, Ce₂O₃0.5-4%.Wherein P₂O₅By NH₄H₂PO₄Or (NH4)₂HPO₄Introduce；Li₂O is introduced by lithium carbonate, Na₂O is introduced by sodium carbonate, K₂O is introduced by potassium carbonate, Tb₂O₃Directly introduce with terbium sesquioxide, Ce₂O₃Direct cerium sesquioxide introduces.Glass batch is added in alumina crucible, a certain temperature after 10-30 minute between 800-1100 DEG C in siliconit stove, glass melt is cast in mixture of ice and water cooling to being pressed into glass flake on roller tablet press, cooling down the purpose to roller tablet press with mixture of ice and water is to improve intensity of cooling, it is easily formed amorphous glass, reduce glass phase-separating and form alkali metal ion race tendency, reduce the probability of fluorescence intensity cancellation.Then in high pressure draught grinds levigate to granularity less than 300nm white fluorescent glass dust.This glass dust, under 254nm and 365nm ultraviolet lighting, all produces the green fluorescence that brightness is the strongest.

It is surface modifier by the fluorescent glass powder prepared, selection white oil, silane coupler, stearic acid or titanate coupling agent, with common plastics, it is blended including polypropylene (PP), polyethylene (PE), polrvinyl chloride (PVC), Merlon (PC), polyester terephthalate (PET) master batch high pressure, the each constituent mass percentage formula scope being blended is: the granularity fluorescent glass powder less than 300nm, 0.5-8%, coupling agent 0.5-2%, master batch 90-99%.Melted co-extrusion pelletize, blown film, it is thus achieved that doped with rare-earth elements Tb³⁺PP, PE, PVC, PC, PET Ultraluminescence film.These plastic foils are about the same with normal film outward appearance in the sunlight, but show bright green fluorescence under ultraviolet lighting, as Anti-counterfeit plastic film base material, have special visible light-transmissive spectrum, it is achieved novel antiforge function.Product can be directly used as Anti-fake packaging film, compound after as anti-fake products such as antifalsification label base material, anti-fake safety lines.

The invention has the beneficial effects as follows:

Phosphate fluorescent glass powder prepared by the present invention, due to Tb³⁺Ion is by [PO₄] the saturated coordination of group, by Tb during high-temperature fusion³⁺Uniform ion is distributed in the melt, Tb in glass³⁺Ion and Tb³⁺Between ion, spacing increases, it is impossible to formed by Tb³⁺The race that ion is formed, does not occur interionic energy of the same race to shift, so not havinging concentration quenching under high doping, fluorescence intensity is with Tb³⁺The increase of amount and increase, on the one hand can improve the incorporation of effective Tb and not produce concentration quenching, on the other hand can give full play to each Tb³⁺The fluorescent functional of ion, obtains the highest fluorescence intensity with minimum Tb incorporation, also reduces cost simultaneously.

Although the f electronics in rare earth element can occur f-f transition under light illumination, but absorptance is little near ultraviolet band, luminous efficiency is low, and suitably phosphate glass substrate is high at extinction coefficient, after they are as ligand and rare-earth ion coordination, if its triplet excited state mates with the excited level of rare earth, then energy is passed to rare earth ion in non-radiative de excitation mode by its triplet excited state after absorbing ultra-violet (UV) band energy by ligand, the rare earth ion being in excited state returns low-lying level with radiation mode transition again, sends rare earth characteristic fluorescence.The energy of triplet should be higher than that the energy of rare earth ion excited state, the excessive or too small fluorescence that all can not obtain high intensity.With Tb³⁺Ion-activated phosphate glass substrate adds a small amount of Ce³⁺, Ce³⁺Tb is given by the excitation energy absorbed transmission³⁺, cause Ce³⁺The luminous intensity quencher of self.So make excitation energy by Ce³⁺It is transferred to Tb^{3 +}, effectively improve its fluorescence emission wavelengths scope, and improve its emission peak intensity so that it is be remarkably reinforced in 618nm feature peak position intensity, reach to strengthen fluorescent effect.

The formula utilizing phosphate alkali metal glass designs, lower the polarity of phosphate glass fluorescent material, add the way of coupling agent simultaneously, reduce the polarity between inorganic fluorescent glass powder and high molecule plastic poor, increase the compatibility of unorganic glass fluorescent material and macromolecule masterbatch melt blending, so that the rare earth high polymer material of preparation has the high transparency and excellent mechanical strength.

A kind of method that doping is simplicity, widely applicable and the suitability is strong.Inorganic doping agent is compared with organic blended dose, and preparation technology is simple, harmless to environment and human body.Overcome organic blended dose of existence and stability difference and to human body and the problem of bad environmental.

Detailed description of the invention

Below in conjunction with embodiment, the invention will be further described.

Embodiment 1

Glass formula conversion is that the oxide of mass percent is: P₂O₅60%；Li₂O 4%；Na₂O 15%；K₂O 15%；Tb₂O₃4%, Ce₂O₃2%.Wherein P₂O₅By NH₄H₂PO₄Introduce；Li₂O is introduced by lithium carbonate, Na₂O is introduced by sodium carbonate, K₂O is introduced by potassium carbonate, Tb₂O₃Directly introduce with terbium sesquioxide, Ce₂O₃Direct cerium sesquioxide introduces.Glass batch is added in alumina crucible, in siliconit stove 900 DEG C insulation 20 minutes after, glass melt is cast in mixture of ice and water cooling to being pressed into glass flake on roller tablet press, then in high pressure draught grinds levigate to granularity less than 300nm white fluorescent glass dust.

It is coupling agent by the fluorescent glass powder prepared, selection white oil, respectively with common plastics, it is blended including a kind of high pressure in polypropylene (PP), polyethylene (PE), polrvinyl chloride (PVC), Merlon (PC), polyester terephthalate (PET) master batch, the formula being blended is: the granularity fluorescent glass powder less than 300nm, 4%, surface modifier 0.5%, plastic master batch 96.5%.Melted co-extrusion pelletize, blown film, it is thus achieved that doped with rare-earth elements PP, PE, PVC, PC, PET Ultraluminescence film of Tb.These plastic foils are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the green fluorescence that brightness is the strongest.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, it is achieved novel antiforge function.Product can be directly used as Anti-fake packaging film, compound after as anti-fake products such as antifalsification label base material, anti-fake safety lines.

Embodiment 2

Glass formula conversion is that the oxide of mass percent is: P₂O₅75%；Na₂O 16%；Tb₂O₃8%, Ce₂O₃1%.Wherein P₂O₅By NH₄H₂PO₄Introduce；K₂O is introduced by potassium carbonate, Na₂O is introduced by sodium carbonate, K₂O is introduced by potassium carbonate, Tb₂O₃Directly introduce with terbium sesquioxide, Ce₂O₃Direct cerium sesquioxide introduces.In siliconit stove 900 DEG C insulation 20 minutes after, glass melt is cast in cool down with mixture of ice and water to being pressed into glass flake on roller tablet press, then high pressure draught grind in levigate to granularity be less than 300nm white fluorescent glass dust.

It is coupling agent by the fluorescent glass powder prepared, selection silane coupler KH570, respectively with common plastics master batch, it is blended including a kind of high pressure in polypropylene (PP), polyethylene (PE), polrvinyl chloride (PVC), Merlon (PC), polyester terephthalate (PET) master batch, the mass percent formula being blended is: the granularity fluorescent glass powder less than 300nm, 0.5%, surfactant 1%, plastic master batch 98.5%.Melted co-extrusion pelletize, blown film, obtain doped with rare-earth elements respectively PP, PE, PVC, PC, PET Ultraluminescence film of Tb.These plastic foils are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the green fluorescence that brightness is the strongest.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, it is achieved novel antiforge function.Product can be directly used as Anti-fake packaging film, compound after as anti-fake products such as antifalsification label base material, anti-fake safety lines.

Embodiment 3

Glass formula conversion is that the oxide of mass percent is: P₂O₅80%；Na₂O 10%；Li₂O 5%；Tb₂O₃3%, Ce₂O₃2%.Wherein P₂O₅By NH₄H₂PO₄Introduce；Na₂O is introduced by sodium carbonate, Tb₂O₃Directly introduce with europiumsesquioxide, Ce₂O₃Direct cerium sesquioxide introduces.Glass batch is added in alumina crucible, in siliconit stove 900 DEG C insulation 30 minutes after, glass melt is cast in cool down with mixture of ice and water to being pressed into glass flake on roller tablet press, then in high pressure draught grinds levigate to granularity less than 300nm white fluorescent glass dust.

It is surface modifier by the fluorescent glass powder prepared, stearic acid, respectively with common plastics, it is blended including a kind of high pressure in polypropylene (PP), polyethylene (PE), polrvinyl chloride (PVC), Merlon (PC), polyester terephthalate (PET) master batch, the formula being blended is: the granularity fluorescent glass powder 8% less than 300nm, surface modifier 2%, plastic master batch 90%.Melted co-extrusion pelletize, blown film, it is thus achieved that PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Tb.These plastic foils are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the green fluorescence that brightness is the strongest.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, it is achieved novel antiforge function.Product can be directly used as Anti-fake packaging film, compound after as anti-fake products such as antifalsification label base material, anti-fake safety lines.

Embodiment 4

Glass formula conversion is that the oxide of mass percent is: P₂O₅78%；Na₂O 10%；K₂O 5%；Tb₂O₃6%, Ce₂O₃1%.Wherein P₂O₅By NH₄H₂PO₄Introduce；Na₂O is introduced by sodium carbonate, K₂O is introduced by potassium carbonate, Tb₂O₃Directly introduce with terbium sesquioxide, Ce₂O₃Direct cerium sesquioxide introduces.Glass batch is added in alumina crucible, in siliconit stove 1100 DEG C insulation 10 minutes after, glass melt is cast in cool down with mixture of ice and water to being pressed into glass flake on roller tablet press, then in high pressure draught grinds levigate to granularity less than 300nm white fluorescent glass dust.

It is surface modifier by the fluorescent glass powder prepared, selection titanate coupling agent TC-114, respectively with common plastics, it is blended including a kind of high pressure in polypropylene (PP), polyethylene (PE), polrvinyl chloride (PVC), Merlon (PC), polyester terephthalate (PET) master batch, the formula being blended is: the granularity fluorescent glass powder 2% less than 300nm, surface modifier 1.5%, plastic master batch 96.5%.Melted co-extrusion pelletize, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Tb respectively.These plastic foils are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the green fluorescence that brightness is the strongest.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, it is achieved novel antiforge function.Product can be directly used as Anti-fake packaging film, compound after as anti-fake products such as antifalsification label base material, anti-fake safety lines.

Embodiment 5

Glass formula conversion is that the oxide of mass percent is: P₂O₅70%；K₂O 23%；Tb₂O₃4%, Ce₂O₃3%.Wherein P₂O₅By (NH₄)₂HPO₄Introduce；K₂O is introduced by potassium carbonate, Tb₂O₃Directly introduce with terbium sesquioxide, Ce₂O₃Direct cerium sesquioxide introduces.Glass batch is added in alumina crucible, in siliconit stove 950 DEG C insulation 10 minutes after, glass melt is cast in cool down with mixture of ice and water to being pressed into glass flake on roller tablet press, then in high pressure draught grinds levigate to granularity less than 300nm white fluorescent glass dust.

By the fluorescent glass powder prepared, select silane coupler KH570 and common plastics, it is blended with a kind of high pressure included in polypropylene (PP), polyethylene (PE), polrvinyl chloride (PVC), Merlon (PC), polyester terephthalate (PET) master batch respectively, the formula being blended is: the granularity fluorescent glass powder 1% less than 300nm, surface modifier 1%, master batch 98%.Melted co-extrusion pelletize, blown film, obtain doped with rare-earth elements respectively PP, PE, PVC, PC, PET Ultraluminescence film of Tb.These plastic foils are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the green fluorescence that brightness is the strongest.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, it is achieved novel antiforge function.Product can be directly used as Anti-fake packaging film, compound after as anti-fake products such as antifalsification label base material, anti-fake safety lines.

Embodiment 6

Glass formula conversion is that the oxide of mass percent is: P₂O₅90%；Na₂O 5.5%；Tb₂O₃4%, Ce₂O₃0.5%.Wherein P₂O₅By (NH₄)₂HPO₄Introduce；Na₂O is introduced by sodium carbonate, Tb₂O₃Directly introduce with terbium sesquioxide, Ce₂O₃Direct cerium sesquioxide introduces.Glass batch is added in alumina crucible, in siliconit stove 1100 DEG C insulation 10 minutes after, glass melt is cast in and cools down being pressed into glass flake on roller tablet press with mixture of ice and water, then in high pressure draught grinds levigate to granularity less than 300nm white fluorescent glass dust.

It is surface modifier by the fluorescent glass powder prepared, selection white oil, respectively with common plastics, it is blended including a kind of high pressure in polypropylene (PP), polyethylene (PE), polrvinyl chloride (PVC), Merlon (PC), polyester terephthalate (PET) master batch, the formula being blended is: the granularity fluorescent glass powder 5% less than 300nm, surface modifier 1%, plastic master batch 90-99%.Melted co-extrusion pelletize, blown film, obtain PP, PE, PVC, PC, PET Ultraluminescence film of doped with rare-earth elements Tb respectively.These plastic foils are about the same with normal film outward appearance in the sunlight, but under 254nm and 365nm ultraviolet lighting, all produce the green fluorescence that brightness is the strongest.As Anti-counterfeit plastic film base material, there is special visible light-transmissive spectrum, it is achieved novel antiforge function.Product can be directly used as Anti-fake packaging film, compound after as anti-fake products such as antifalsification label base material, anti-fake safety lines.

Claims (4)

1. a preparation method for the green plastic sheeting of Ultraluminescence being light toner with RE phosphate glass, its feature It is, comprises the following steps:

The first step, prepares containing rare earth Tb with high-temperature melting method³⁺And Ce³⁺Phosphate glass fluorescent material, phosphorus Silicate glass formula is converted to mass percent oxide: P₂O₅50-90%, Li₂O0-10%, Na₂O 5-25%, K₂O0-15%, Tb₂O₃1-15%, Ce₂O₃0.5-4%；Wherein P₂O₅By NH₄H₂PO₄Or (NH₄)₂HPO₄Introduce, Li₂O is introduced by lithium carbonate, Na₂O is introduced by sodium carbonate, K₂O is introduced by potassium carbonate, Tb₂O₃Directly introduce with terbium sesquioxide, Ce₂O₃Direct cerium sesquioxide introduces；By various raw materials by joining After side's uniformly mixing, a certain temperature in 800-1100 DEG C 10-30 minute, vitreous humour is cast in use Mixture of ice and water cooling to roller tablet press tabletting after, be broken to particle mean size by airflow milling high-pressure powder and be less than 300nm；By each component of phosphate glass in formula, and Tb³⁺And Ce³⁺Cooperative effect, with frozen water mix Compound cooling glass, to roller tablet press, improves intensity of cooling, overcomes fluorescence intensity quenching phenomenon, improve rare earth Element T b³⁺Addition and fluorescence efficiency, fluorescent material has special Ultraluminescence spectrum；

Second step, mixes phosphate glass fluorescent material with conventional macromolecular material master batch, and adds surface and change Property agent, each component calculates by mass percentage: granularity is less than the glass fluorescent material 0.5-8% of 300nm, surface Modifying agent 0.5-2%, master batch 90-99%；Melt blending preparation has the fluorescent green of special Ultraluminescence spectrum Plastic sheeting, overcomes the polymer base material impact on rare-earth fluorescent, and Ultraluminescence luminous efficiency is high, fluorescence By force.

The most according to claim 1 a kind of with RE phosphate glass be light toner the green plastics of Ultraluminescence thin The preparation method of film, is characterized in that the polymer master batch described in second step, refers to polypropylene or polyethylene or poly- Any one in vinyl chloride or Merlon or polyester terephthalate.

The most according to claim 1 a kind of with RE phosphate glass be light toner the green plastics of Ultraluminescence thin The preparation method of film, is characterized in that the surface modifier described in second step, refer to white oil or silane coupler or One in stearic acid or titanate coupling agent.

4. with RE phosphate glass be light toner the green plastic sheeting of Ultraluminescence in the application of false proof aspect, Described plastic sheeting preparation method according to claim 1 is prepared from, outside it is in the sunlight with normal film As sight, white clear, but under 254nm and 365nm ultraviolet lighting, the green all producing brightness the strongest is glimmering Light, and there is special visible light-transmissive spectrum, it is directly used as Anti-fake packaging film or antifalsification label printing base Material or anti-fake safety line base material.